Aquatic silicone passive samplers are increasingly used to measure hydrophobic micropollutant concentrations, such as polychlorobiphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and polycyclic aromatic hydrocarbons (PAHs), because of their high sampling rate. However, extraction is often time- and resource-consuming, usually done by traditional solvent-based techniques followed by column chromatography clean-up. This study assessed the potential of accelerated solvent extraction (ASE) for simultaneous extraction and clean-up of silicone passive samplers for large-scale monitoring of hydrophobic contaminants. Nine ASE methods were tested with hexane and dichloromethane as extraction solvents and silica gel and aluminium oxide as clean-up adsorbents. Recovery rates for the three compound families were 10-20% lower than with Soxhlet extraction followed by column chromatography clean-up. The method using 25 g of adsorbents (1:1 w:w), a 3:1 hexane/dichloromethane solvent ratio and a temperature of 103°C was chosen for its high recovery rates, low variability and low solvent and adsorbent use. This ASE method halved extraction time compared to Soxhlet extraction and was successfully tested on field-deployed passive samplers with relative recovery rates around 80% compared to Soxhlet, and relative standard deviation (%RSD) around 30%. Its application on the monitoring of 21 sampling sites in the Geneva Lake Basin showed satisfying results, with median relative errors of 11% on sampling rates (and extrapolated water concentration), compared to 7% for the Soxhlet method. The slightly lower concentrations did not impact the detection of pollution problems. The developed ASE method proved to be more efficient than Soxhlet extraction in the monitoring of hydrophobic compounds.
Water pollution from agricultural, industrial, and urban activities poses a significant threat to ecosystems and human health. Traditional water monitoring methods, such as active sampling, often provide limited temporal resolution and/or spatial coverage. As an alternative, this study explores the use of passive sampling within a forensic operational monitoring framework to assess river pollution. Passive samplers were deployed across three rivers in Switzerland with diverse land-use profiles, to collect time-weighted average concentrations of various micropollutants, including pesticides, pharmaceuticals and industrial chemicals. These micropollutants were viewed as traces of anthropogenic activities. The collected data were integrated into a memory that enabled the detection of spatial and temporal pollution patterns and the formulation of hypotheses on potential contamination sources.This forensic intelligence framework provided a structured, iterative process for both monitoring and investigative purposes. The integration of passive sampling data within an operational monitoring cycle facilitated continuous data acquisition across multiple sites, allowing for an in-depth spatio-temporal assessment of river pollution. The memory component enabled systematic pattern detection, linking specific pollution profiles to land use types such as agriculture, industrial, and urban zones. By supporting hypothesis testing and refinement over time, the forensic monitoring framework offered a dynamic tool not only to detect pollution trends but also to identify their sources, potentially guiding timely and targeted environmental actions. This methodology highlights the utility of forensic science in environmental monitoring, providing actionable intelligence for stakeholders to enhance water quality management and inform adaptive policy interventions in response to recurring pollution events.
The present study investigates the long-term immobilization efficiency of biochar on target per- and polyfluoroalkyl substances (PFAS) and precursors in well-drained soils contaminated by aqueous film-forming foam (AFFF) (Ʃ27PFAS = 1624 ± 276 µg/kg) over 2 years. The total oxidizable precursor (TOP) assay revealed a large precursor reservoir in the soil. Fifteen outdoor field-scale columns were packed with contaminated soil (48 kg) without (control columns, triplicates) and with biochar amendments: Three sewage sludge-based biochars were homogeneously mixed into the soil at a 1% (w/w) dose in triplicate columns. One of the biochars was additionally applied as a barrier at the column base (1% w/w) in a separate set of columns. The best-performing biochar immobilized long-chain PFAS by 91.0 ± 35.0% and short-chain PFAS by 96.7 ± 32.9%, possibly due to a well-developed porosity. Compared to the control columns, the fluctuating PFAS leaching were negligible in columns amended with the best-performing biochar, but the immobilization efficiency of short-chain PFAS decreased after one year (from 97.8% to 74.2%). Applying biochar as a barrier was two times more effective than homogenous mixing, and the effect was most pronounced for long-chain PFAS. Our findings suggest that biochar may immobilize precursors, notably CF3-CF5 precursors, to the same extent or better than their typical target perfluoroalkyl acids transformation products. More research is, however, needed to confirm these trends. Going beyond simple lab experiments, this study suggests that biochar is a promising solution for PFAS remediation and brings the technology closer to field application.
Passive sampling offers a promising approach for assessing contaminants in surface waters; however, its broader adoption is limited by the need for standardized and user-friendly implementation methods and the availability of suitable sorbents. This study investigates the performance of the widely used Empore™ SDB-RPS disk and two potential alternative sorbent phases-Affinisep AttractSPE® HLB (AHLB) and Biotage Atlantic® HLB-L (BHLB)-for the uptake of >100 pesticides with diverse physicochemical properties (logKOW = -2 to 5, pKa = -3.15 to 12.58) and compares them against the Empore SDB-RPS disk. The passive sampler (PS) performance was evaluated under controlled laboratory settings using a flow system at environmentally relevant conditions (21 cm/s, 300 ng/L, 2-week exposure) and an established open-source stainless-steel housing. Diffusive transport characteristics were assessed by determining relative resistances of the water boundary layer and the sorbent to the mass transfer, with average sorbent resistance (1/Rs, tot) contributions ranging from 39% and 40% (AHLB and SDB-RPS) to 87% (BHLB). Performance under field conditions was assessed through a 2-week calibration alongside active sampling in an agricultural stream (22-40 cm/s). Pesticide accumulation was linear to curvilinear (monotonically increasing) for all PSs, despite uptake being partially (AHLB and SDB-RPS) or almost completely (BHLB) controlled by the sorbent. The uptake of pesticides to all PSs could be well described by a simple first-order uptake model as opposed to more complex approaches, such as incorporating fluctuating water concentrations or diffusion models. Laboratory sampling rates (Rs) could be determined for 78% of pesticides. Comparable results were observed for AHLB (Rs average = 0.42 ± 0.24 L/day) and SDB-RPS (Rs average = 0.41 ± 0.27 L/day), whereas BHLB showed lower rates (on average, a factor of 5 lower). Field evaluations confirmed the similar capabilities of AHLB to SDB-RPS, detecting ≥43 of the studied pesticides, while BHLB detected fewer (29 pesticides), likely due to its fiberglass structure acting as additional resistance. For all sorbents and compounds with available sampling rates (>50% of detected compounds in the field), time-weighted average concentrations derived from PS closely matched active sampling measurements between 0.5 and 2.5 times, supporting their reliability for pesticide quantification. Overall, this study provides recoveries, sampling rates, and sampler-water partition coefficients (Ksw) for three PSs for a range of pesticides. This work helps to facilitate the broader adoption of passive sampling techniques for regulatory and environmental analysis.
InfoMetricsFiguresRef. Journal of Agricultural and Food ChemistryASAPArticle This publication is Open Access under the license indicated. Learn More CiteCitationCitation and abstractCitation and referencesMore citation options ShareShare onFacebookX (Twitter)WeChatLinkedInRedditEmailJump toExpandCollapse ViewpointJanuary 29, 2025A Virtuous Cycle of Phytoremediation, Pyrolysis, and Biochar Applications toward Safe PFAS Levels in Soil, Feed, and FoodClick to copy article linkArticle link copied!Gerard Cornelissen*Gerard CornelissenNorwegian Geotechnical Institute (NGI), Oslo 0484, NorwayNorwegian University of Life Sciences (NMBU), Ås 1432, Norway*[email protected]More by Gerard Cornelissenhttps://orcid.org/0000-0003-2033-9514Nathalie BrielsNathalie BrielsARCHE Consulting, Ghent 9032, BelgiumMore by Nathalie Brielshttps://orcid.org/0000-0002-1310-3004Thomas D. BucheliThomas D. BucheliEnvironmental Analytics, Agroscope, Zürich 8046, SwitzerlandMore by Thomas D. Buchelihttps://orcid.org/0000-0001-9971-3104Nicolas EstoppeyNicolas EstoppeyNorwegian Geotechnical Institute (NGI), Oslo 0484, NorwayMore by Nicolas EstoppeyAndrea GredeljAndrea GredeljNorwegian Geotechnical Institute (NGI), Oslo 0484, NorwayMore by Andrea Gredeljhttps://orcid.org/0000-0001-7766-871XNikolas HagemannNikolas HagemannEnvironmental Analytics, Agroscope, Zürich 8046, SwitzerlandIthaka Institute, Goldbach 63773, GermanyMore by Nikolas HagemannSylvain LerchSylvain LerchRuminant Nutrition and Emissions, Agroscope, Posieux 1725, SwitzerlandMore by Sylvain Lerchhttps://orcid.org/0000-0003-0957-8012Simon LotzSimon LotzIthaka Institute, Arbaz 1974, SwitzerlandMore by Simon LotzDaniel RasseDaniel RasseNorwegian Institute for Bioeconomy (NIBIO), Ås 1432, NorwayMore by Daniel Rassehttps://orcid.org/0000-0002-5977-3863Hans-Peter SchmidtHans-Peter SchmidtIthaka Institute, Arbaz 1974, SwitzerlandMore by Hans-Peter Schmidthttps://orcid.org/0000-0001-8275-7506Erlend SørmoErlend SørmoNorwegian Geotechnical Institute (NGI), Oslo 0484, NorwayNorwegian University of Life Sciences (NMBU), Ås 1432, NorwayMore by Erlend Sørmohttps://orcid.org/0000-0002-3345-8777Hans Peter H. ArpHans Peter H. ArpNorwegian Geotechnical Institute (NGI), Oslo 0484, NorwayNorwegian University of Science and Technology (NTNU), Trondheim 7491, NorwayMore by Hans Peter H. Arphttps://orcid.org/0000-0002-0747-8838Open PDFJournal of Agricultural and Food ChemistryCite this: J. Agric. Food Chem. 2025, XXXX, XXX, XXX-XXXClick to copy citationCitation copied!https://pubs.acs.org/doi/10.1021/acs.jafc.5c00651https://doi.org/10.1021/acs.jafc.5c00651Published January 29, 2025 Publication History Received 14 January 2025Published online 29 January 2025article-commentary© 2025 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0 . 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Attribution (BY): Credit must be given to the creator.View full license *DisclaimerThis summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials. License Summary*You are free to share(copy and redistribute) this article in any medium or format and to adapt(remix, transform, and build upon) the material for any purpose, even commercially within the parameters below: Creative Commons (CC): This is a Creative Commons license. Attribution (BY): Credit must be given to the creator. View full license *DisclaimerThis summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials. License Summary*You are free to share(copy and redistribute) this article in any medium or format and to adapt(remix, transform, and build upon) the material for any purpose, even commercially within the parameters below: Creative Commons (CC): This is a Creative Commons license. Attribution (BY): Credit must be given to the creator. View full license *DisclaimerThis summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials. ACS Publications© 2025 The Authors. Published by American Chemical SocietySubjectswhat are subjectsArticle subjects are automatically applied from the ACS Subject Taxonomy and describe the scientific concepts and themes of the article.BeveragesBiomassCropsPyrolysisSoilsPFAS in AgricultureClick to copy section linkSection link copied!Farmlands can be contaminated with per- and polyfluorinated alkylated substances (PFAS) from increased levels in biosolids, compost, digestate, and animal manure. Such contamination can lead to high and persistent PFAS levels in (ground)water, crops, milk, and meat, (1) increasing human dietary exposure.Phytoremediation, Pyrolysis, and Biochar AmendmentClick to copy section linkSection link copied!Remediation of PFAS-impacted agricultural soil is challenging because of the diffuse character of the pollution. (2) Destructive approaches (soil washing, excavation, incineration, and chemical oxidation) will impair soil ecosystem services and cause carbon emissions. (2) In situ methods such as phytoremediation (3) and sorbent amendment with carbonaceous and/or ion-exchanging materials (4) are less intrusive and more cost-effective. (2,3) Phytoremediation of PFAS has been demonstrated to be a cost-effective, environmentally friendly, energy efficient, and aesthetically pleasing option. (3) However, high variabilities were observed between the uptake potential of different PFAS and between plant species. (3,5) Pyrolysis can mineralize the PFAS in the phytoremediation biomass, (6) providing a win–win solution in which PFAS is eliminated from biomass (6) and other biosolids (7) through pyrolysis, generating biochar. This is a sustainable sorbent material (4,8) with co-benefits in terms of carbon sequestration (1–2 t of CO2 equivalents/t of biochar (9)), sustainable waste management, (2,6) and energy generation during pyrolysis. (2)A Virtuous CycleClick to copy section linkSection link copied!We propose a virtuous cycle by using phytoremediation for the accumulation of short-chain PFAS, destroying them by pyrolytic treatment, and applying the resulting PFAS-free biochar as a sorbent to immobilize long-chain PFAS (Figure 1). Pyrolyzing the contaminated plant biomass alleviates the constraints of biomass disposal. The proposed cycle takes advantage of the high phytoextraction potential for (ultra)short-chain PFAS, which are less strongly sorbed to biochar. We further suggest that the addition of biochar to forages may reduce the uptake and bioavailability of PFAS, thereby reducing PFAS contamination in milk and meat.Figure 1Figure 1. Phytoremediation–pyrolysis–biochar virtuous cycle including biochar-amended soil and ruminant feed.High Resolution ImageDownload MS PowerPoint SlideTo optimize the combined remediation by this cycle, pyrolysis probably needs to be conducted above 800 °C to ensure PFAS destruction (6) and sufficient size of the pores in the biochar (>2 nm (4,10)) to sorb PFAS molecules (>1.5 nm (8)). Amendment with 1% sludge biochar or (activated) high-T wood biochar reduced the level of leaching of perfluorooctanesulfonate (PFOS) from contaminated soil by up to 92–99%, (8,10) with notably better effectiveness for long-chain than for short-chain (C4–5) PFAS (40–70% (8)).Roughly 5 t of dry weight (dw) (ha of grass)−1 year–1, approximately one-third of the total harvest, could be turned into 1 t of biochar to be applied on 1 ha per year. Acquiring enough biochar to amend the top 20 cm of a soil (ρ = 1.3 g cm–3) with 1% biochar would then take ∼25 years. Using co-pyrolysis with alternative feedstocks such as manure, (11) crop residues, biosolids, (7,8) or reeds (10) could shorten this time frame. Assuming a biochar price of € 1000 t–1, the cost would be € 25 000 ha–1 plus the cost of the incorporation into the soil plus the cost of fodder yield losses. The overall cost would be lower than that of more intrusive methods (2) and could further be reduced by incorporating carbon credits of up to € 150 (t of CO2)−1 by 2030. (11,12)Optimizing PFAS PhytoremediationClick to copy section linkSection link copied!The effectiveness of PFAS phytoremediation strongly depends on the local conditions and the bioaccumulation factors (BAFs) of the PFAS in the particular soil–plant system. The BAF ranges from ∼10 for short-chain PFBS and PFBA to ∼1 for long-chain PFOS and PFOA. (13) Phytoremediation times with 5 t of dw plant harvest ha–1 year–1 are on the order of 50–500 years, underscoring the need to identify hyperaccumulator crops with high BAFs. Such crops will reduce the phytoremediation time for short-chain PFAS to below a few dozen years, (13) on the same order of magnitude as the time needed to harvest enough biomass to administer 1% biochar.Biochar-Amended Fodder to Reduce the Levels of PFAS in Meat and MilkClick to copy section linkSection link copied!Biochar administration may improve animal health as well as meat and milk production. (12) Ruminants have been fed approximately 100–400 g of biochar day–1 while consuming 10 kg of dw grass day–1. (12) Biochar reduces PFAS bioaccessibility and thus uptake in the digestive tract, resulting in a reduced level of accumulation in body tissues, reducing chronic animal health risk as well as PFAS levels in milk and meat. Biochar–water distribution ratios, Kd, reach 106 L kg–1 for PFOS, (8) far above grass–water Kd's (20–50 L kg–1). (13) Thus, biochar could reduce the PFOS bioavailability in the digestive tract by ≤700-fold. Actual reductions may be less due to (i) incomplete fodder–biochar mixing in the rumen and intestine, (ii) natural organic matter reducing the biochar Kd, (8) (iii) weaker sorption of short-chain PFAS to biochar, (8) (iv) 250 g of biochar day–1 being too little to "depurate" PFAS from a 500 kg ruminant, (14,15) and (v) digestive fluids increasing PFAS chemical activity. (14) Conversely, the slightly acidic rumen environment (pH 5.8) could weaken the electrostatic repulsion between the biochar and the PFAS polar headgroups. (4) Also, digested biochar present in manure could play a role in further sorbing PFAS as well as increasing soil fertility. (12)Restoration of PFAS-Contaminated FarmlandClick to copy section linkSection link copied!Pyrolyzing the entire harvest should be considered a last resort for farmland too contaminated for crop and fodder production. Alternatively, converting only 10–20% of the harvested biomass into biochar could reduce PFAS availability more gradually, offering a long-term solution with climate co-benefits while not compromising farmer income, especially with compensation payments. (16)There are indications that biochar amendments could be effective over increased time scales. The matrix itself is >80% stable for millennia, (9) and the sorption strength can increase with time due to slow diffusion into deeper narrow biochar pores (8) and incorporation into soil aggregates. (17)The best solution for preventing PFAS contamination of farmland is to prevent it ever entering; however, for already compromised land, application of a phytoremediation–pyrolysis–biochar virtuous cycle could help restore soil quality. Optimization should be done by long-term field trials, including various herbage species and agroforestry approaches and varying pyrolysis conditions. Hyperaccumulators could be grown on 10–20% of the land, pyrolyzed and back-applied, after which grass would be reseeded. Remediation of the entire land would then be achieved after a decade.Author InformationClick to copy section linkSection link copied!Corresponding AuthorGerard Cornelissen - Norwegian Geotechnical Institute (NGI), Oslo 0484, Norway; Norwegian University of Life Sciences (NMBU), Ås 1432, Norway; https://orcid.org/0000-0003-2033-9514; Email: [email protected]AuthorsNathalie Briels - ARCHE Consulting, Ghent 9032, Belgium; https://orcid.org/0000-0002-1310-3004Thomas D. Bucheli - Environmental Analytics, Agroscope, Zürich 8046, Switzerland; https://orcid.org/0000-0001-9971-3104Nicolas Estoppey - Norwegian Geotechnical Institute (NGI), Oslo 0484, NorwayAndrea Gredelj - Norwegian Geotechnical Institute (NGI), Oslo 0484, Norway; https://orcid.org/0000-0001-7766-871XNikolas Hagemann - Environmental Analytics, Agroscope, Zürich 8046, Switzerland; Ithaka Institute, Goldbach 63773, GermanySylvain Lerch - Ruminant Nutrition and Emissions, Agroscope, Posieux 1725, Switzerland; https://orcid.org/0000-0003-0957-8012Simon Lotz - Ithaka Institute, Arbaz 1974, SwitzerlandDaniel Rasse - Norwegian Institute for Bioeconomy (NIBIO), Ås 1432, Norway; https://orcid.org/0000-0002-5977-3863Hans-Peter Schmidt - Ithaka Institute, Arbaz 1974, Switzerland; https://orcid.org/0000-0001-8275-7506Erlend Sørmo - Norwegian Geotechnical Institute (NGI), Oslo 0484, Norway; Norwegian University of Life Sciences (NMBU), Ås 1432, Norway; https://orcid.org/0000-0002-3345-8777Hans Peter H. Arp - Norwegian Geotechnical Institute (NGI), Oslo 0484, Norway; Norwegian University of Science and Technology (NTNU), Trondheim 7491, Norway; https://orcid.org/0000-0002-0747-8838NotesThe authors declare no competing financial interest.ReferencesClick to copy section linkSection link copied! This article references 17 other publications. 1Jha, G.; Kankarla, V.; McLennon, E.; Pal, S.; Sihi, D.; Dari, B.; Diaz, D.; Nocco, M. Per-and polyfluoroalkyl substances (PFAS) in integrated crop–livestock systems: environmental exposure and human health risks. Int. J. Environ. Res. Public Health 2021, 18 (23), 12550, DOI: 10.3390/ijerph182312550 Google ScholarThere is no corresponding record for this reference.2Mahinroosta, R.; Senevirathna, L. A review of the emerging treatment technologies for PFAS contaminated soils. J. Environ. Manage. 2020, 255, 109896, DOI: 10.1016/j.jenvman.2019.109896 Google Scholar2A review of the emerging treatment technologies for PFAS contaminated soilsMahinroosta, Reza; Senevirathna, LalanthaJournal of Environmental Management (2020), 255 (), 109896CODEN: JEVMAW; ISSN:0301-4797. (Elsevier Ltd.) A review. Contamination of soils with poly- and perfluoroalkyl substances (PFAS) has become a challenging issue due to the adverse effects of these substances on both the environment and public health. PFAS have strong chem. structures and their bonding with soil makes them challenging to eliminate from soil environments. Traditional methods of soil remediation have not been successful in their redn. or removal from the environment. This paper provides a comprehensive evaluation of existing and emerging technologies for remediating PFAS contaminated soils with guidance on which approach to use in different contexts. The functions of all remediation technologies, their suitability, limitations, and the scale applied from lab. to the field are presented as a baseline for understanding the research need for treatment in soil environments. To date, the immobilization method has been a significant part of the remediation soln. for PFAS contaminated soils, although its long-term efficiency still needs further investigation. Soil washing and thermal treatment techniques have been tested at the field scale, but they are expensive and energy-intensive due to the use of a large vol. of washing solvent and the high m.p. of PFAS, resp.; both methods need a large initial investment for their installation. Other remediation technologies, such as chem. oxidn., ball milling, and electron beams, have been progressed in the lab. However, addnl. research is needed to make them feasible, cost-effective and applicable in the field. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitlehu7jF&md5=6ada5e90a8dd3ce1e82820711956bfc73Mayakaduwage, S.; Ekanayake, A.; Kurwadkar, S.; Rajapaksha, A. U.; Vithanage, M. Phytoremediation prospects of per-and polyfluoroalkyl substances: a review. Environ. Res. 2022, 212, 113311, DOI: 10.1016/j.envres.2022.113311 Google ScholarThere is no corresponding record for this reference.4Liang, D.; Li, C.; Chen, H.; Sørmo, E.; Cornelissen, G.; Gao, Y.; Reguyal, F.; Sarmah, A.; Ippolito, J.; Kammann, C. A critical review of biochar for the remediation of PFAS-contaminated soil and water. Sci. Total Environ. 2024, 951, 174962– 174962, DOI: 10.1016/j.scitotenv.2024.174962 Google ScholarThere is no corresponding record for this reference.5Gredelj, A.; Polesel, F.; Trapp, S. Model-based analysis of the uptake of perfluoroalkyl acids (PFAAs) from soil into plants. Chemosphere 2020, 244, 125534, DOI: 10.1016/j.chemosphere.2019.125534 Google Scholar5Model-based analysis of the uptake of perfluoroalkyl acids (PFAAs) from soil into plantsGredelj, Andrea; Polesel, Fabio; Trapp, StefanChemosphere (2020), 244 (), 125534CODEN: CMSHAF; ISSN:0045-6535. (Elsevier Ltd.) Perfluoroalkyl acids (PFAAs) bioaccumulate in crops, with uptake being particularly high for short-chain PFAAs that are constantly transported with transpiration water to aerial plant parts. Due to their amphiphilic surfactant nature and ionized state at environmental pH, predicting the partitioning behavior of PFAAs is difficult and subject to considerable uncertainty, making exptl. data highly desirable. Here, we applied a plant uptake model that combines advective flux with measured partition coeffs. to reproduce the set of empirically derived plant uptake and soil-partitioning data for nine PFAAs in red chicory, in order to improve the mechanistic understanding and provide new insights into the complex uptake processes. We introduced a new parameter for retarded uptake (R) to explain the slow transfer of PFAA across biomembranes of the root epidermis, which has led to low transpiration stream concn. factors (TSCFs) presented in literature so far. We estd. R values for PFAAs using exptl. data derived for red chicory and used the modified plant uptake model to simulate uptake of PFAA into other crops. Results show that this semi-empirical model predicted PFAAs transport to shoots and fruits with good accuracy based on exptl. root to soil concn. factors (RCFdw) and soil to water partition coeffs. (Kd) as well as estd. R values and plant-specific data for growth and transpiration. It can be concluded that the combination of rather low Kd with high RCFdw and the absence of any relevant loss are the reason for the obsd. excellent plant uptake of PFAAs. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXisVSksbrI&md5=657613d4b354772609c9d37321b775646Sørmo, E.; Castro, G.; Hubert, M.; Licul-Kucera, V.; Quintanilla, M.; Asimakopoulos, A. G.; Cornelissen, G.; Arp, H. P. H. The decomposition and emission factors of a wide range of PFAS in diverse, contaminated organic waste fractions undergoing dry pyrolysis. J. Hazard. Mater. 2023, 454, 131447, DOI: 10.1016/j.jhazmat.2023.131447 Google ScholarThere is no corresponding record for this reference.7Morales, M.; Arp, H. P. H.; Castro, G.; Asimakopoulos, A. G.; Sørmo, E.; Peters, G.; Cherubini, F. Eco-toxicological and climate change effects of sludge thermal treatments: Pathways towards zero pollution and negative emissions. J. Hazard. Mater. 2024, 470, 134242, DOI: 10.1016/j.jhazmat.2024.134242 Google ScholarThere is no corresponding record for this reference.8Sørmo, E.; Lade, C. B. M.; Zhang, J.; Asimakopoulos, A. G.; Åsli, G. W.; Hubert, M.; Goranov, A. I.; Arp, H. P. H.; Cornelissen, G. Stabilization of PFAS-contaminated soil with sewage sludge-and wood-based biochar sorbents. Sci. Total Environ. 2024, 922, 170971, DOI: 10.1016/j.scitotenv.2024.170971 Google ScholarThere is no corresponding record for this reference.9Schmidt, H. P.; Anca-Couce, A.; Hagemann, N.; Werner, C.; Gerten, D.; Lucht, W.; Kammann, C. Pyrogenic carbon capture and storage. GCB Bioenergy 2019, 11 (4), 573– 591, DOI: 10.1111/gcbb.12553 Google ScholarThere is no corresponding record for this reference.10Liu, N.; Wu, C.; Lyu, G.; Li, M. Efficient adsorptive removal of short-chain perfluoroalkyl acids using reed straw-derived biochar (RESCA). Sci. Total Environ. 2021, 798, 149191, DOI: 10.1016/j.scitotenv.2021.149191 Google Scholar10Efficient adsorptive removal of short-chain perfluoroalkyl acids using reed straw-derived biochar (RESCA)Liu, Na; Wu, Chen; Lyu, Guifen; Li, MengyanScience of the Total Environment (2021), 798 (), 149191CODEN: STENDL; ISSN:0048-9697. (Elsevier B.V.) Drinking water and groundwater treatment of perfluoroalkyl acids (PFAAs) heavily relies on adsorption-based approaches using carbonaceous materials, such as granular activated carbon (GAC). Application of GAC is restricted by its inefficiency to remove short-chain PFAAs that have prevalently emerged as substitutes and/or metabolites of long-chain polyfluoroalkyl and perfluoroalkyl substances (PFAS). Here, we synthesized reed straw-derived biochar (RESCA) exhibiting exceptional removal efficiencies (>92%) toward short-chain PFAAs at environment-relevant concns. (e.g., 1μg/L). Pseudo-second-order kinetic consts. of RESCA were 1.13 and 1.23 L/(mg h) for perfluorobutanoic acid (PFBA) and perfluorobutanesulfonic acid (PFBS), resp., over six times greater than GAC. SEM imaging and BET anal. revealed the combination of highly hydrophobic surface and scattered distribution of mesopores (2-10 nm in diam.) was assocd. with the rapid adsorption of short-chain PFAAs. RESCA-packed filters demonstrated effective removal of the mixt. of three short-chain and three long-chain PFAAs in the influent with the flow rate up to 45 mL/min. In contrast, GAC-packed filters were significantly less efficient in the removal of short-chain PFAAs, which were also neg. affected by the increase of the flow rate. Efficacy of RESCA-packed filters was also validated in four PFAA-spiked groundwater samples from different sites. Dissolved org. matter (DOC) of >8 mg/L can neg. affect the removal of short-chain PFAAs by RESCA. Feasibility of scaling up the RESCA adsorption system was investigated using breakthrough simulation. Overall, RESCA represents a green adsorbent alternative for the feasible and scalable treatment of a wide spectrum of PFAAs of different chain lengths and functional moieties. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhs1yqsbzL&md5=f6bfad91650a39d7d37ebdf7aea9c3be11Rathnayake, D.; Schmidt, H. P.; Leifeld, J.; Mayer, J.; Epper, C. A.; Bucheli, T. D.; Hagemann, N. Biochar from animal manure: A critical assessment on technical feasibility, economic viability, and ecological impact. GCB Bioenergy 2023, 15 (9), 1078– 1104, DOI: 10.1111/gcbb.13082 Google ScholarThere is no corresponding record for this reference.12Schmidt, H.-P.; Hagemann, N.; Draper, K.; Kammann, C. The use of biochar in animal feeding. PeerJ 2019, 7, e7373 DOI: 10.7717/peerj.7373 Google ScholarThere is no corresponding record for this reference.13Lesmeister, L.; Lange, F. T.; Breuer, J.; Biegel-Engler, A.; Giese, E.; Scheurer, M. Extending the knowledge about PFAS bioaccumulation factors for agricultural plants–A review. Sci. Total Environ. 2021, 766, 142640, DOI: 10.1016/j.scitotenv.2020.142640 Google Scholar13Extending the knowledge about PFAS bioaccumulation factors for agricultural plants - A reviewLesmeister, Lukas; Lange, Frank Thomas; Breuer, Joern; Biegel-Engler, Annegret; Giese, Evelyn; Scheurer, MarcoScience of the Total Environment (2021), 766 (), 142640CODEN: STENDL; ISSN:0048-9697. (Elsevier B.V.) A review. A main source of perfluoroalkyl and polyfluoroalkyl substances (PFASs) residues in agricultural plants is their uptake from contaminated soil. Bioaccumulation factors (BAFs) can be an important tool to derive recommendations for cultivation or handling of crops prior consumption. This review compiles >4500 soil-to-plant BAFs for 45 PFASs from 24 studies involving 27 genera of agricultural crops. Grasses (Poaceae) provided most BAFs with the highest no. of values for perfluorooctanoic acid and perfluorooctane sulfonic acid. Influencing factors on PFAS transfer like compd.-specific properties (hydrophobicity, chain length, functional group, etc.), plant species, compartments, and other boundary conditions are critically discussed. Throughout the literature, BAFs were higher for vegetative plant compartments than for reproductive and storage organs. Decreasing BAFs per addnl. perfluorinated carbon were clearly apparent for aboveground parts (up to 1.16 in grains) but not always for roots (partly down to zero). Combining all BAFs per single perfluoroalkyl carboxylic acid (C4-C14) and sulfonic acid (C4-C10), median log BAFs decreased by -0.25(±0.029) and -0.24(±0.013) per fluorinated carbon, resp. For the first time, the plant uptake of ultra-short-chain (≤ C3) perfluoroalkyl acids (PFAAs) was reviewed and showed a ubiquitous occurrence of trifluoroacetic acid in plants independent from the presence of other PFAAs. Based on identified knowledge gaps, it is suggested to focus on the uptake of precursors to PFAAs, PFAAs ≤C3, and addnl. emerging PFASs such as GenX or fluorinated ethers in future research. Studies regarding the uptake of PFASs by sugar cane, which accounts for about one fifth of the global crop prodn., are completely lacking and are also recommended. Furthermore, aq. soil leachates should be tested as an alternative to the solvent extn. of soils as a base for BAF calcns. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitFSmsrbM&md5=b3649aaabb2470c0d8db2f92dfb3f41c14Hilber, I.; Arrigo, Y.; Zuber, M.; Bucheli, T. D. Desorption resistance of polycyclic aromatic hydrocarbons in biochars incubated in cow ruminal liquid in vitro and in vivo. Environ. Sci. Technol. 2019, 53 (23), 13695– 13703, DOI: 10.1021/acs.est.9b04340 Google ScholarThere is no corresponding record for this reference.15Lastel, M.-L.; Fournier, A.; Jurjanz, S.; Thomé, J.-P.; Joaquim-Justo, C.; Archimède, H.; Mahieu, M.; Feidt, C.; Rychen, G. Comparison of chlordecone and NDL-PCB decontamination dynamics in growing male kids after cessation of oral exposure: Is there a potential to decrease the body levels of these pollutants by dietary supplementation of activated carbon or paraffin oil?. Chemosphere 2018, 193, 100– 107, DOI: 10.1016/j.chemosphere.2017.10.120 Google ScholarThere is no corresponding record for this reference.16Werner, C.; Schmidt, H.-P.; Gerten, D.; Lucht, W.; Kammann, C. Biogeochemical potential of biomass pyrolysis systems for limiting global warming to 1.5 C. Environ. Res. Lett. 2018, 13 (4), 044036, DOI: 10.1088/1748-9326/aabb0e Google ScholarThere is no corresponding record for this reference.17Obia, A.; Mulder, J.; Martinsen, V.; Cornelissen, G.; Borresen, T. In situ effects of biochar on aggregation, water retention and porosity in light-textured tropical soils. Soil Tillage Res. 2016, 155, 35– 44, DOI: 10.1016/j.still.2015.08.002 Google ScholarThere is no corresponding record for this reference.Cited By Click to copy section linkSection link copied!This article has not yet been cited by other publications.Download PDFFiguresReferences Get e-AlertsGet e-AlertsJournal of Agricultural and Food ChemistryCite this: J. Agric. Food Chem. 2025, XXXX, XXX, XXX-XXXClick to copy citationCitation copied!https://doi.org/10.1021/acs.jafc.5c00651Published January 29, 2025 Publication History Received 14 January 2025Published online 29 January 2025© 2025 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0 . 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Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.Recommended Articles FiguresReferencesAbstractHigh Resolution ImageDownload MS PowerPoint SlideFigure 1Figure 1. Phytoremediation–pyrolysis–biochar virtuous cycle including biochar-amended soil and ruminant feed.High Resolution ImageDownload MS PowerPoint SlideReferences This article references 17 other publications. 1Jha, G.; Kankarla, V.; McLennon, E.; Pal, S.; Sihi, D.; Dari, B.; Diaz, D.; Nocco, M. Per-and polyfluoroalkyl substances (PFAS) in integrated crop–livestock systems: environmental exposure and human health risks. Int. J. Environ. Res. Public Health 2021, 18 (23), 12550, DOI: 10.3390/ijerph182312550 There is no corresponding record for this reference.2Mahinroosta, R.; Senevirathna, L. A review of the emerging treatment technologies for PFAS contaminated soils. J. Environ. Manage. 2020, 255, 109896, DOI: 10.1016/j.jenvman.2019.109896 2A review of the emerging treatment technologies for PFAS contaminated soilsMahinroosta, Reza; Senevirathna, LalanthaJournal of Environmental Management (2020), 255 (), 109896CODEN: JEVMAW; ISSN:0301-4797. (Elsevier Ltd.) A review. Contamination of soils with poly- and perfluoroalkyl substances (PFAS) has become a challenging issue due to the adverse effects of these substances on both the environment and public health. PFAS have strong chem. structures and their bonding with soil makes them challenging to eliminate from soil environments. Traditional methods of soil remediation have not been successful in their redn. or removal from the environment. This paper provides a comprehensive evaluation of existing and emerging technologies for remediating PFAS contaminated soils with guidance on which approach to use in different contexts. The functions of all remediation technologies, their suitability, limitations, and the scale applied from lab. to the field are presented as a baseline for understanding the research need for treatment in soil environments. To date, the immobilization method has been a significant part of the remediation soln. for PFAS contaminated soils, although its long-term efficiency still needs further investigation. Soil washing and thermal treatment techniques have been tested at the field scale, but they are expensive and energy-intensive due to the use of a large vol. of washing solvent and the high m.p. of PFAS, resp.; both methods need a large initial investment for their installation. Other remediation technologies, such as chem. oxidn., ball milling, and electron beams, have been progressed in the lab. However, addnl. research is needed to make them feasible, cost-effective and applicable in the field. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitlehu7jF&md5=6ada5e90a8dd3ce1e82820711956bfc73Mayakaduwage, S.; Ekanayake, A.; Kurwadkar, S.; Rajapaksha, A. U.; Vithanage, M. Phytoremediation prospects of per-and polyfluoroalkyl substances: a review. Environ. Res. 2022, 212, 113311, DOI: 10.1016/j.envres.2022.113311 There is no corresponding record for this reference.4Liang, D.; Li, C.; Chen, H.; Sørmo, E.; Cornelissen, G.; Gao, Y.; Reguyal, F.; Sarmah, A.; Ippolito, J.; Kammann, C. A critical review of biochar for the remediation of PFAS-contaminated soil and water. Sci. Total Environ. 2024, 951, 174962– 174962, DOI: 10.1016/j.scitotenv.2024.174962 There is no corresponding record for this reference.5Gredelj, A.; Polesel, F.; Trapp, S. Model-based analysis of the uptake of perfluoroalkyl acids (PFAAs) from soil into plants. Chemosphere 2020, 244, 125534, DOI: 10.1016/j.chemosphere.2019.125534 5Model-based analysis of the uptake of perfluoroalkyl acids (PFAAs) from soil into plantsGredelj, Andrea; Polesel, Fabio; Trapp, StefanChemosphere (2020), 244 (), 125534CODEN: CMSHAF; ISSN:0045-6535. (Elsevier Ltd.) Perfluoroalkyl acids (PFAAs) bioaccumulate in crops, with uptake being particularly high for short-chain PFAAs that are constantly transported with transpiration water to aerial plant parts. Due to their amphiphilic surfactant nature and ionized state at environmental pH, predicting the partitioning behavior of PFAAs is difficult and subject to considerable uncertainty, making exptl. data highly desirable. Here, we applied a plant uptake model that combines advective flux with measured partition coeffs. to reproduce the set of empirically derived plant uptake and soil-partitioning data for nine PFAAs in red chicory, in order to improve the mechanistic understanding and provide new insights into the complex uptake processes. We introduced a new parameter for retarded uptake (R) to explain the slow transfer of PFAA across biomembranes of the root epidermis, which has led to low transpiration stream concn. factors (TSCFs) presented in literature so far. We estd. R values for PFAAs using exptl. data derived for red chicory and used the modified plant uptake model to simulate uptake of PFAA into other crops. Results show that this semi-empirical model predicted PFAAs transport to shoots and fruits with good accuracy based on exptl. root to soil concn. factors (RCFdw) and soil to water partition coeffs. (Kd) as well as estd. R values and plant-specific data for growth and transpiration. It can be concluded that the combination of rather low Kd with high RCFdw and the absence of any relevant loss are the reason for the obsd. excellent plant uptake of PFAAs. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXisVSksbrI&md5=657613d4b354772609c9d37321b775646Sørmo, E.; Castro, G.; Hubert, M.; Licul-Kucera, V.; Quintanilla, M.; Asimakopoulos, A. G.; Cornelissen, G.; Arp, H. P. H. The decomposition and emission factors of a wide range of PFAS in diverse, contaminated organic waste fractions undergoing dry pyrolysis. J. Hazard. Mater. 2023, 454, 131447, DOI: 10.1016/j.jhazmat.2023.131447 There is no corresponding record for this reference.7Morales, M.; Arp, H. P. H.; Castro, G.; Asimakopoulos, A. G.; Sørmo, E.; Peters, G.; Cherubini, F. Eco-toxicological and climate change effects of sludge thermal treatments: Pathways towards zero pollution and negative emissions. J. Hazard. Mater. 2024, 470, 134242, DOI: 10.1016/j.jhazmat.2024.134242 There is no corresponding record for this reference.8Sørmo, E.; Lade, C. B. M.; Zhang, J.; Asimakopoulos, A. G.; Åsli, G. W.; Hubert, M.; Goranov, A. I.; Arp, H. P. H.; Cornelissen, G. Stabilization of PFAS-contaminated soil with sewage sludge-and wood-based biochar sorbents. Sci. Total Environ. 2024, 922, 170971, DOI: 10.1016/j.scitotenv.2024.170971 There is no corresponding record for this reference.9Schmidt, H. P.; Anca-Couce, A.; Hagemann, N.; Werner, C.; Gerten, D.; Lucht, W.; Kammann, C. Pyrogenic carbon capture and storage. GCB Bioenergy 2019, 11 (4), 573– 591, DOI: 10.1111/gcbb.12553 There is no corresponding record for this reference.10Liu, N.; Wu, C.; Lyu, G.; Li, M. Efficient adsorptive removal of short-chain perfluoroalkyl acids using reed straw-derived biochar (RESCA). Sci. Total Environ. 2021, 798, 149191, DOI: 10.1016/j.scitotenv.2021.149191 10Efficient adsorptive removal of short-chain perfluoroalkyl acids using reed straw-derived biochar (RESCA)Liu, Na; Wu, Chen; Lyu, Guifen; Li, MengyanScience of the Total Environment (2021), 798 (), 149191CODEN: STENDL; ISSN:0048-9697. (Elsevier B.V.) Drinking water and groundwater treatment of perfluoroalkyl acids (PFAAs) heavily relies on adsorption-based approaches using carbonaceous materials, such as granular activated carbon (GAC). Application of GAC is restricted by its inefficiency to remove short-chain PFAAs that have prevalently emerged as substitutes and/or metabolites of long-chain polyfluoroalkyl and perfluoroalkyl substances (PFAS). Here, we synthesized reed straw-derived biochar (RESCA) exhibiting exceptional removal efficiencies (>92%) toward short-chain PFAAs at environment-relevant concns. (e.g., 1μg/L). Pseudo-second-order kinetic consts. of RESCA were 1.13 and 1.23 L/(mg h) for perfluorobutanoic acid (PFBA) and perfluorobutanesulfonic acid (PFBS), resp., over six times greater than GAC. SEM imaging and BET anal. revealed the combination of highly hydrophobic surface and scattered distribution of mesopores (2-10 nm in diam.) was assocd. with the rapid adsorption of short-chain PFAAs. RESCA-packed filters demonstrated effective removal of the mixt. of three short-chain and three long-chain PFAAs in the influent with the flow rate up to 45 mL/min. In contrast, GAC-packed filters were significantly less efficient in the removal of short-chain PFAAs, which were also neg. affected by the increase of the flow rate. Efficacy of RESCA-packed filters was also validated in four PFAA-spiked groundwater samples from different sites. Dissolved org. matter (DOC) of >8 mg/L can neg. affect the removal of short-chain PFAAs by RESCA. Feasibility of scaling up the RESCA adsorption system was investigated using breakthrough simulation. Overall, RESCA represents a green adsorbent alternative for the feasible and scalable treatment of a wide spectrum of PFAAs of different chain lengths and functional moieties. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhs1yqsbzL&md5=f6bfad91650a39d7d37ebdf7aea9c3be11Rathnayake, D.; Schmidt, H. P.; Leifeld, J.; Mayer, J.; Epper, C. A.; Bucheli, T. D.; Hagemann, N. Biochar from animal manure: A critical assessment on technical feasibility, economic viability, and ecological impact. GCB Bioenergy 2023, 15 (9), 1078– 1104, DOI: 10.1111/gcbb.13082 There is no corresponding record for this reference.12Schmidt, H.-P.; Hagemann, N.; Draper, K.; Kammann, C. The use of biochar in animal feeding. PeerJ 2019, 7, e7373 DOI: 10.7717/peerj.7373 There is no corresponding record for this reference.13Lesmeister, L.; Lange, F. T.; Breuer, J.; Biegel-Engler, A.; Giese, E.; Scheurer, M. Extending the knowledge about PFAS bioaccumulation factors for agricultural plants–A review. Sci. Total Environ. 2021, 766, 142640, DOI: 10.1016/j.scitotenv.2020.142640 13Extending the knowledge about PFAS bioaccumulation factors for agricultural plants - A reviewLesmeister, Lukas; Lange, Frank Thomas; Breuer, Joern; Biegel-Engler, Annegret; Giese, Evelyn; Scheurer, MarcoScience of the Total Environment (2021), 766 (), 142640CODEN: STENDL; ISSN:0048-9697. (Elsevier B.V.) A review. A main source of perfluoroalkyl and polyfluoroalkyl substances (PFASs) residues in agricultural plants is their uptake from contaminated soil. Bioaccumulation factors (BAFs) can be an important tool to derive recommendations for cultivation or handling of crops prior consumption. This review compiles >4500 soil-to-plant BAFs for 45 PFASs from 24 studies involving 27 genera of agricultural crops. Grasses (Poaceae) provided most BAFs with the highest no. of values for perfluorooctanoic acid and perfluorooctane sulfonic acid. Influencing factors on PFAS transfer like compd.-specific properties (hydrophobicity, chain length, functional group, etc.), plant species, compartments, and other boundary conditions are critically discussed. Throughout the literature, BAFs were higher for vegetative plant compartments than for reproductive and storage organs. Decreasing BAFs per addnl. perfluorinated carbon were clearly apparent for aboveground parts (up to 1.16 in grains) but not always for roots (partly down to zero). Combining all BAFs per single perfluoroalkyl carboxylic acid (C4-C14) and sulfonic acid (C4-C10), median log BAFs decreased by -0.25(±0.029) and -0.24(±0.013) per fluorinated carbon, resp. For the first time, the plant uptake of ultra-short-chain (≤ C3) perfluoroalkyl acids (PFAAs) was reviewed and showed a ubiquitous occurrence of trifluoroacetic acid in plants independent from the presence of other PFAAs. Based on identified knowledge gaps, it is suggested to focus on the uptake of precursors to PFAAs, PFAAs ≤C3, and addnl. emerging PFASs such as GenX or fluorinated ethers in future research. Studies regarding the uptake of PFASs by sugar cane, which accounts for about one fifth of the global crop prodn., are completely lacking and are also recommended. Furthermore, aq. soil leachates should be tested as an alternative to the solvent extn. of soils as a base for BAF calcns. >> More from SciFinder ®https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitFSmsrbM&md5=b3649aaabb2470c0d8db2f92dfb3f41c14Hilber, I.; Arrigo, Y.; Zuber, M.; Bucheli, T. D. Desorption resistance of polycyclic aromatic hydrocarbons in biochars incubated in cow ruminal liquid in vitro and in vivo. Environ. Sci. Technol. 2019, 53 (23), 13695– 13703, DOI: 10.1021/acs.est.9b04340 There is no corresponding record for this reference.15Lastel, M.-L.; Fournier, A.; Jurjanz, S.; Thomé, J.-P.; Joaquim-Justo, C.; Archimède, H.; Mahieu, M.; Feidt, C.; Rychen, G. Comparison of chlordecone and NDL-PCB decontamination dynamics in growing male kids after cessation of oral exposure: Is there a potential to decrease the body levels of these pollutants by dietary supplementation of activated carbon or paraffin oil?. Chemosphere 2018, 193, 100– 107, DOI: 10.1016/j.chemosphere.2017.10.120 There is no corresponding record for this reference.16Werner, C.; Schmidt, H.-P.; Gerten, D.; Lucht, W.; Kammann, C. Biogeochemical potential of biomass pyrolysis systems for limiting global warming to 1.5 C. Environ. Res. Lett. 2018, 13 (4), 044036, DOI: 10.1088/1748-9326/aabb0e There is no corresponding record for this reference.17Obia, A.; Mulder, J.; Martinsen, V.; Cornelissen, G.; Borresen, T. In situ effects of biochar on aggregation, water retention and porosity in light-textured tropical soils. Soil Tillage Res. 2016, 155, 35– 44, DOI: 10.1016/j.still.2015.08.002 There is no corresponding record for this reference.
This paper presents an approach to apply aquatic passive sampling (PS) in regulatory chemical water quality monitoring in Europe. Absorption-based passive sampling is well developed and suitable for the sampling of hydrophobic chemicals, some of which are European Water Framework Directive priority substances with Environmental Quality Standards (EQS) derived for biota.Considering a chemical activity approach to chemical risk assessment, we propose equilibrium concentration in lipids (from passive water sampling) as a reference value for measured concentrations in biota. Through existing PS-fish datasets, we show a growing body of evidence supporting the use of lipid-based contaminant concentrations at equilibrium with water derived from PS as a conservative proxy of levels of these chemicals in fish.We propose a procedure that includes PS as a first, animal-free screening step of a tiered approach, followed by more conventional fish analyses when PS indicates these are needed to confirm EQSbiota exceedance. This paper reviews fish-passive sampler datasets, provides a reasoning for the proposed procedure and discusses how to broadly put it into monitoring practice. PS offers the possibility of well-defined standardised monitoring approaches that can help overcome the natural variability challenges associated with measurements in biota across member states and simplify EQSbiota compliance.
Measuring dissolved concentrations of polybrominated diphenyl ethers (PBDEs) and non-BDE flame retardants on a global scale provides critical insights into the effectiveness of the Stockholm Convention. In the present study, we deployed passive sampling devices at 43 seawater and freshwater sites covering 21 countries from 2016 to 2020. The detection frequencies were 20-94% for BDE congeners and 33-42% for dechlorane plus, higher than those (0-20%) for other target compounds. The median concentrations of dissolved Σ9PBDE (sum of BDE-28, -47, -66, -85, -99, -100, -153, -154, and -183) were 0.28 and 0.64 pg L-1 in seawater and freshwater, respectively. The concentrations of dissolved Σ9PBDE, along with published data, slightly increased before 2016 and remained steady from 2016 to 2018, indicating delayed effects of the global phaseout of technical Penta- and Octa-BDEs. The log-transformed concentrations of individual BDE congeners were better correlated with regional gross domestic product than with population density. The potential ecological risk of BDE-47 was low, and there was a lack of key risk indicators for other compounds. The present study documented the delayed response of the aquatic environment to the regulatory actions on reducing PBDE emissions.
Bio-based fertilizers (BBFs) produced from organic waste contribute to closed-loop nutrient cycles and circular agriculture. However, persistent organic contaminants, such as per- and poly-fluoroalkyl substances (PFAS), polychlorobiphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), as well as polyaromatic hydrocarbons (PAHs) can be present in organic waste or be formed during valorization processes. Consequently, these hazardous substances may be introduced into agricultural soils and the food chain via BBFs. This study assessed the exposure of 84 target substances and extractable organic fluorine (EOF) in 19 BBFs produced from different types of waste, including agricultural and food industrial waste, sewage sludge, and biowaste, and through various types of valorization methods, including hygienization at low temperatures (<150 °C) as well as pyrolysis and incineration at elevated temperatures (150–900 °C). The concentrations in BBFs (ΣPFOS & PFOA: <30 μg kg−1, Σ6PCBs: <15 μg kg−1, Σ11PAHs: <3 mg kg−1, Σ17PCDD/Fs: <4 ng TEQ kg−1) were found to be below the strictest thresholds used in individual EU countries, with only one exception (pyrolyzed sewage sludge, Σ11PAHs: 5.9 mg kg−1). Five BBFs produced from sewage sludge or chicken manure contained high concentrations of EOF (>140 μg kg−1), so monitoring of more PFAS is recommended. The calculated expected concentrations in soils after one BBF application (e.g. PFOS: <0.05 μg kg−1) fell below background contamination levels (PFOS: 2.7 μg kg−1) elsewhere in the literature. This was confirmed by the analysis of BBF-amended soils from field experiments (Finland and Austria). Studies on target legacy contaminants in sewage sludge were reviewed, indicating a general decreasing trend in concentration with an apparent half-life ranging from 4 (PFOS) to 9 (PCDD/Fs) years. Modelled cumulative concentrations of the target contaminants in agricultural soils indicated low long-term risks. Concentrations estimated and analyzed in cereal grains were low, indicating that exposure by cereal consumption is well below tolerable daily intakes.
Bio-based fertilizers (BBFs) produced from organic waste have the potential to reduce societal dependence on limited and energy -intensive mineral fertilizers. BBFs, thereby, contribute to a circular economy for fertilizers. However, BBFs can contain plastic fragments and hazardous additives such as phthalate plasticizers, which could constitute a risk for agricultural soils and the environment. This study assessed the exposure associated with plastic and phthalates in BBFs from three types of organic wastes: agricultural and food industry waste (AgriFoodInduWaste), sewage sludge (SewSludge), and biowaste (i.e., garden, park, food and kitchen waste). The wastes were associated with various treatments like drying, anaerobic digestion, and vermicomposting. The number of microplastics (0.045-5 mm) increased from AgriFoodInduWaste-BBFs (15-258 particles g(- 1)), to SewSludge-BBFs (59-1456 particles g(- 1)) and then to Biowaste-BBFs (828-2912 particles g- 1). Biowaste-BBFs mostly contained packaging plastics (e.g., polyethylene terephthalate), with the mass of plastic (>10 g kg( - 1)) exceeding the EU threshold (3 g kg( - 1), plastics >2 mm). Other BBFs mostly contained small (< 1 mm) nonpackaging plastics in amounts below the EU limit. The calculated numbers of microplastics entering agricultural soils via BBF application was high (10(7)-10(10) microplastics ha- 1y- 1), but the mass of plastic released from AgriFoodInduWaste-BBFs and SewSludge-BBFs was limited (< 1 and <7 kg ha(- 1)y(- 1)) compared to Biowaste-BBFs (95-156 kg ha(- 1)y(- 1)). The concentrations of di(2-ethylhexyl)phthalate (DEHP; < 2.5 mg kg( - 1)) and phthalate transformation products (< 8 mg kg( - 1)) were low (< benchmark of 50 mg kg( - 1) for DEHP), attributable to both the current phase -out of DEHP as well as phthalate degradation during waste treatment. The Biowaste-BBF exposed to vermicomposting indicated that worms accumulated phthalate transformation products (4 mg kg( - 1)). These results are overall positive for the implementation of the studied AgriFoodInduWaste-BBFs and SewSludge-BBFs. However, the safe use of the studied Biowaste-BBFs requires reducing plastic use and improving sorting methods to minimize plastic contamination, in order to protect agricultural soils and reduce the environmental impact of Biowaste-BBFs.
Polycyclic aromatic hydrocarbons (PAHs), released from petrogenic, pyrogenic or diagenetic sources (degradation of wood materials), are of global concern due to their adverse effects, and potential for long-range transport. While dissolved PAHs have been frequently reported in the literature, there has been no consistent approach of sampling across water bodies. Passive samplers from the AQUA/GAPS-MONET initiative were deployed at 46 sites (28 marine and 18 freshwater), and analyzed for 28 PAHs and six polycyclic musks (PCMs) centrally. Freely dissolved PAH concentrations were dominated by phenanthrene (mean concentration 1500 pg L-1; median 530 pg L-1) and other low molecular weight compounds. Greatest concentrations of phenanthrene, fluoranthene, and pyrene were typically from the same sites, mostly in Europe and North America. Of the PCMs, only galaxolide (72% of samples) and tonalide (61%) were regularly detected, and were significantly cross-correlated. Benchmarking of PAHs relative to penta- and hexachlorobenzene confirmed that the most remote sites (Arctic, Antarctic, and mountain lakes) displayed below average PAH concentrations. Concentrations of 11 of 28 PAHs, galaxolide and tonalide were positively correlated (P < 0.05) with population density within a radius of 5 km of the sampling site. Characteristic PAH ratios gave conflicting results, likely reflecting multiple PAH sources and postemission changes.
Passive samplers are key tools to sample hydrophilic micropollutants in water. Two main approaches address the influence of hydrodynamics: (1) determining site-specific sampling rate ( R S ) by characterizing k w , the mass transfer coefficient of the water-boundary layer (WBL), and (2) reducing WBL impact using a diffusive material to control the uptake. The first requires calibration data and the second has only been achieved using fragile diffusive material. This study assesses the transfer of hydrophilic contaminants through polytetrafluoroethylene (PTFE; 30 mu m thick), a new membrane material with lower sorption than commonly used polyethersulfone (PES). Combined for the first time in a Chemcatcher-like configuration, we calibrated the modified samplers for 44 micropollutants to provide R S - k w relationships for in-situ R S determination (approach 1). Micropollutants accumulated over 2000 times more on the sorbent than on PTFE. PTFE-based R S (0.027 to 0.300 L day -1 ) were 2.5 higher than previously reported with PES. Membrane property measurements (porosity, tortuosity) indicated that accumulation is primarily controlled by the membrane. Extrapolation indicated that using thicker PTFE membranes ( >= 100 mu m) would shift uptake control entirely to the membrane in river conditions (approach 2). This finding could enable R S prediction based on contaminants properties, thus representing a significant advancement in passive sampling.
Persistent organic pollutants (POPs) are recognized as pollutants of global concern, but so far, information on the trends of legacy POPs in the waters of the world has been missing due to logistical, analytical, and financial reasons. Passive samplers have emerged as an attractive alternative to active water sampling methods as they accumulate POPs, represent time-weighted average concentrations, and can easily be shipped and deployed. As part of the AQUA-GAPS/MONET, passive samplers were deployed at 40 globally distributed sites between 2016 and 2020, for a total of 21 freshwater and 40 marine deployments. Results from silicone passive samplers showed α-hexachlorocyclohexane (HCH) and γ-HCH displaying the greatest concentrations in the northern latitudes/Arctic Ocean, in stark contrast to the more persistent penta (PeCB)- and hexachlorobenzene (HCB), which approached equilibrium across sampling sites. Geospatial patterns of polychlorinated biphenyl (PCB) aqueous concentrations closely matched original estimates of production and use, implying limited global transport. Positive correlations between log-transformed concentrations of Σ7PCB, ΣDDTs, Σendosulfan, and Σchlordane, but not ΣHCH, and the log of population density (p < 0.05) within 5 and 10 km of the sampling sites also supported limited transport from used sites. These results help to understand the extent of global distribution, and eventually time-trends, of organic pollutants in aquatic systems, such as across freshwaters and oceans. Future deployments will aim to establish time-trends at selected sites while adding to the geographical coverage.
Water contamination is a growing concern in society. New environmental laws are being enacted to define intolerable human activities, and their enforcement is increasingly supported by forensic science. However, water contamination is a broader security issue that is not only caused by illegal human behavior. Risk‐based approaches are needed to prevent (re)occurrence of incidents and minimize their negative consequences. This can be achieved through the formalization of a monitoring process producing intelligence (i.e., actionable knowledge), crucial to detect recurring incidents, and guiding decision‐makers in their choice of preventive and responsive actions. In this perspective, forensic science has a key role to play in integrating vestiges from water‐contaminating activities (i.e., traces) in such a problem‐solving process. Information conveyed by traces allows detecting similarities among contamination events (i.e., patterns), inferring common causes, and better understanding of mechanisms and consequences of water contamination. The different stages of the process will be described and illustrated through a real case example. Current barriers to the implementation of such a process are then discussed, showing how systemic issues and complexity may prevent the establishment of links across contamination events, thus negatively impacting the generation of intelligence. To overcome these obstacles, we underline the importance to initiate local and size‐limited approaches by implementing relatively simple and flexible systems. New knowledge can be used to improve local situations and help stakeholders to understand the benefits of such a process; then, by a bottom‐up iterative learning process, the approach can be given a greater ambition at a larger scale. This article is categorized under: Forensic Science in Action/Crime Scene Investigation > Special Situations and Investigations Crime Scene Investigation > From Traces to Intelligence and Evidence Forensic Chemistry and Trace Evidence > Forensic Food and Environment Analysis
Integrative passive sampling is particularly useful in the monitoring of hydrophilic contaminants in surface water, but the impact of hydrodynamics on contaminant uptake still needs to be better considered. In part A (Glanzmann et al., 2023), Chemcatcher-like hydrophilic samplers (i.e., SDB-RPS extraction disks covered by PES microporous membranes) were calibrated to determine the sampling rates RS of 44 hydrophilic contaminants (pesticides, pharmaceuticals, industrial products) taking into account the hydrodynamic conditions. In this study, Chemcatcher-like passive sampling devices that allowed co-deploying hydrophilic samplers and performance reference compounds (PRC)-spiked silicone disks were tested in a Swiss river with intermediate water velocities (5-50 cm s-1, 23 cm s-1 on average) during 11 consecutive 14-day periods. The PRC dissipation from silicone disks - combined with the calibration data from part A - allowed to determine in-situ RS that took into account hydrodynamic conditions. The obtained aqueous time-weighted average (TWA) concentrations were found to be robust with good concordance between duplicates (mean quotient of 1.16 between the duplicates). For most measurements (76 %), TWA concentrations showed no major difference (20 cm s-1). RS from the literature (RS,LIT) - obtained at water velocities between 8 and 37 cm s-1 - were also shown to provide comparable TWA concentrations in the studied hydrodynamic conditions (average water velocity of 24 cm s-1). The estimated errors due to the use of RS,MAX or RS,LIT rather than in-situ RS are given as a function of the water velocity to determine in which conditions the developed method is required (or not) in monitoring programs.
When monitoring water quality with hydrophilic integrative passive sampling devices, it is crucial to use accurate sampling rates (RS) that account for exposure conditions such as hydrodynamics. This study aims at calibrating Chemcatcher-like passive samplers - styrene-divinylbenzene reverse phase sulfonate (SDB-RPS) extraction disk covered by a polyethersulfone (PES) membrane - at four water flow velocities (5 to 40 cm s-1) in a channel system. First, the four hydrodynamic conditions were characterized by measuring the mass transfer coefficients of the water boundary layer (kw) at the surface of the samplers using the alabaster dissolution method. Then, fifty-six samplers were deployed in the channels and exposed for 7 different intervals varying from 1 to 21 days. Thus, RS were determined at four different kw for 44 hydrophilic compounds, ranging from 0.015 to 0.115 L day-1. Relationships were established between kw and RS using models for mixed rate control by the membrane and the water boundary layer. The estimated parameters of those relationships are suitable for the determination of accurate RS when kw is measured in situ, for example by co-deploying silicone disks spiked with performance and reference compounds (PRC) as implemented in Part B.
The issue of microplastic (MP) litter in the aquatic environment and its capability of accumulating and/or releasing pollutants has been brought to light in recent years. Biodegradable plastics have been proposed as one of the different solutions to decrease environmental input of discarded plastics; however, their ability to accumulate and release pollutants once in the marine environment has not been assessed yet. In this study, we compare the accumulation and the release of a wide range of compounds by biodegradable (polyhydroxyalkanoates (PHA) and polybutylene succinate (PBS)) and conventional (polyethylene (PE)) MPs following exposure to natural seawater for 64 days. We quantified polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organophosphorus flame retardants (PFRs), phthalates, and alternative plasticizers in MPs, before and after exposure. Results indicated that PBS- and PHA-MPs accumulated the largest amount of PAHs and PFRs, respectively. Leaching of PFRs and plasticizers was observed for all polymers and was approximately twofold greater for PE- when compared to PBS- and PHA-MPs. Overall, our study suggests that biodegradable MPs may release less additives and accumulate a larger amount of contaminants from seawater compared to conventional ones: these findings may have implications on the risk assessment of biodegradable polymers for marine biota; and on potential widespread adoption of these types of plastics.
Passive sampling devices (PSDs) offer key benefits for monitoring chemical water quality, but the uptake process of PSDs for hydrophilic compounds still needs to be better understood. Determining mass transfer coefficients of the water boundary layer (kw) during calibration experiments and in situ monitoring would contribute toward achieving this; it allows for combining calibration data obtained at different temperature and hydrodynamic conditions and facilitate the translation of laboratory-derived calibration data to field exposure. This study compared two kw measurement methods applied to extraction disk housings (Chemcatcher), namely, alabaster dissolution and dissipation of performance reference compounds (PRCs) from silicone. Alabaster- and PRC-based kw were measured at four flow velocities (5-40 cm s-1) and two temperatures (11 and 20 °C) in a channel system. Data were compared using a relationship based on Sherwood, Reynolds, and Schmidt numbers. Good agreement was observed between data obtained at both temperatures, and for the two methods. Data were well explained by a model for mass transfer to a flat plate under laminar flow. It was slightly adapted to provide a semi-empirical model accounting for the effects of housing design on hydrodynamics. The use of PRC-spiked silicone to obtain in situ integrative kw for Chemcatcher-type PSDs is also discussed.
A first test of the field capabilities of a novel in situ sampling technique combining active and passive sampling (APS) was conducted in the sea. The proof-of-concept device uses a pump to draw water into a diffusion cell where dissolved target substances are accumulated onto sorbents which are selective for different classes of contaminants (i.e., metal cations, polar and non-polar organic compounds), simultaneously. A controlled laminar flow established in the diffusion cell enables measurements of contaminant concentrations that are fully independent from the hydrodynamic conditions in the bulk solution. APS measurements were consistent with those obtained using conventional passive sampling techniques such as organic diffusive gradients in thin films (o-DGT) and silicone rubber (SR) samplers (generally < 40% difference), taking into account the prevailing hydrodynamic conditions. The use of performance reference compounds (PRC) for hydrophobic contaminants provided additional information. Field measurements of metal ions in seawater showed large variability due to issues related to the device configuration. An improved field set-up deployed in supplementary freshwater mesocosm experiments provided metal speciation data that was consistent with passive sampling measurements (DGT), taking into account the hydrodynamic conditions. Overall, the results indicate that the APS technique provides a promising approach for the determination of a wide range of contaminants simultaneously, and independently from the hydrodynamic conditions in the bulk solution.
Forensic soil examination has a well-established foundation in forensic science, this is in part due to the widely varied and complex nature of soil. Within this domain, mineral suite studies are a commonly utilized tool in soil examination. However, statistical or probabilistic approaches towards the interpretation of re-sults from such analysis are lacking and this study aims to fill that gap. Soil samples from four different locations in the city of Lausanne, Switzerland were sampled and their mineral fractions, light and heavy of size between 90 and 180 mu m, were studied utilizing microscopical methods. First, the light minerals were identified and counted by employing scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDS). Second, the heavy minerals were identified and counted manually under a po-larized light microscope (PLM). The resulting count data were subjected to various multivariate statistical treatments such as principal components analysis (PCA), hierarchical clustering analysis (HCA), and linear discriminant analysis (LDA). These methods assist in identifying pertinent variables and subsequently in building various classification models. The validities of these models were then tested and evaluated using blind tests. Finally, these methods demonstrate how a probabilistic approach can be taken in the inter-pretation of the results to answer source level questions. (c) 2021 The Authors. Published by Elsevier B.V.
Between 1920 and 1967, approximatively 8200 tons of ammunition waste were dumped into some Swiss lakes. This study is part of the extensive historical and technical investigations performed since 1995 by Swiss authorities to provide a risk assessment. It aims to assess whether explosive monitoring by passive sampling is feasible in lake-bottom waters. Polar organic chemical integrative sampler (POCIS) and Chemcatcher were first calibrated in a channel system supplied with continuously refreshed lake water spiked with two nitroamines (HMX and RDX), one nitrate ester (PETN), and six nitroaromatics (including TNT). Exposure parameters were kept as close as possible to the ones expected at the bottom of two affected lakes. Sixteen POCIS and Chemcatcher were simultaneously deployed in the channel system and removed in duplicates at 8 different intervals over 21 days. Sorbents and polyethersulfone (PES) membranes were separately extracted and analyzed by UPLC-MS/MS. When possible, a three-compartment model was used to describe the uptake of compounds from water, over the PES membrane into the sorbent. Uptake of target compounds by sorbents was shown not to approach equilibrium during 21 days. However, nitroaromatics strongly accumulated in PES, thus delaying the transfer of these compounds to sorbents (lag-phase up to 9 days). Whereas sampling rate (R-S) of nitroamines were in the range of 0.06-0.14 L day(-1), R-S of nitroaromatics were up to 10 times lower. As nitroaromatic accumulation in PES was integrative over 21 days, PES was used as receiving phase for these compounds. The samplers were then deployed at lake bottoms. To ensure that exposure conditions were similar between calibration and field experiments, low-density polyethylene strips spiked with performance reference compounds were co-deployed in both experiments and dissipation data were compared. Integrative concentrations of explosives measured in the lakes confirmed results obtained by previous studies based on grab sampling. (C) 2019 Elsevier Ltd. All rights reserved.